WO2009111076A2 - Metal recovery - Google Patents
Metal recovery Download PDFInfo
- Publication number
- WO2009111076A2 WO2009111076A2 PCT/US2009/001470 US2009001470W WO2009111076A2 WO 2009111076 A2 WO2009111076 A2 WO 2009111076A2 US 2009001470 W US2009001470 W US 2009001470W WO 2009111076 A2 WO2009111076 A2 WO 2009111076A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rhenium
- acid
- catalyst
- titania
- cobalt
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/026—Obtaining nickel or cobalt by dry processes from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to the recovery of catalytic metals on a solid titania support and in particular to the recovery of rhenium from titania supported Fischer-Tropsch catalysts.
- Catalysts comprising a catalytically active metal on a support such as silica or alumina are known in the art for hydrogenation reactions.
- a catalyst comprising platinum and rhenium supported on alumina has been found to be highly effective for the reforming of naphtha.
- a catalyst comprising cobalt and rhenium supported on alumina or silica has been found to be effective for the preparation of hydrocarbons from synthesis gas via the Fischer-Tropsch process.
- rhenium is an expensive metal, its excellent catalyst promoting activity justifies its commercial use.
- a catalytic metal or metals on a titania support.
- cobalt and rhenium supported on titania is preferred by some workers for Fischer-Tropsch reactions because it is more active for CO conversion than when supported on alumina or silica.
- titania supported catalysts may be preferred for use in hydrothermal environments where alumina supports may show a tendency to degrade to some extent.
- catalysts tend to become less active and require periodic regeneration. Regeneration typically restores the activity of the catalyst to a level approximating its original condition; however, after many regenerations, the catalyst will no longer be capable of being restored to a satisfactory activity level. It then becomes necessary to replace the deactivated or spent catalyst with fresh catalyst.
- An object of the present invention is to provide a method for the recovery of rhenium from titania-supported catalysts and especially the recovery of cobalt and rhenium from titania-supported cobalt and rhenium catalysts.
- the present invention provides a method for recovering rhenium from a titania-supported rhenium-containing catalyst, such as a rhenium-promoted cobalt catalyst, the method comprising treating the catalyst in the reduced form with an acid in an amount and for a time sufficient to dissolve the rhenium without dissolving the support.
- cobalt and rhenium metals are recovered from a titania-supported cobalt and rhenium-promoted metal catalyst by treating the catalyst in its reduced form with an acid in an amount and for a time sufficient to dissolve the catalytic metals and thereafter separating the dissolved metals from the undissolved support.
- the present invention is applicable to catalysts containing rhenium supported on a titania catalyst support.
- rhenium-containing catalyst is used broadly herein to include rhenium and also rhenium combined with other catalytic metals such as Group VII noble metals, for example, platinum, palladium, rhodium, osmium, iridium and ruthenium; and non-noble metals, such as, cobalt, nickel, and iron.
- the present invention is particularly applicable to titania-supported cobalt and rhenium catalysts such as those used in the Fischer-Tropsch hydrocarbon synthesis process. Therefore, for convenience, the present invention will be described by specific reference to titania-supported cobalt and rhenium catalysts.
- the catalyst treated according to the invention normally will be a used catalyst that has become at least partially spent or deactivated.
- rhenium can be recovered from fresh catalyst as well by the process of the invention.
- a reducing atmosphere for example, a hydrogen-containing atmosphere
- a slurry of spent, rhenium-containing, titania-supported catalyst in liquid hydrocarbons is separated from the hydrocarbons in a catalyst separation zone.
- the separated catalyst then is contacted with hydrogen or a mixture of hydrogen and an inert gas at temperatures in the range of about
- a slurry of spent, rhenium-containing, titania-supported catalyst in the liquid hydrocarbons may be reduced in the presence of the liquid hydrocarbons by contacting the slurry with H2 and CO in the molar ratio of about 1.5 to 4.0 at pressures of 1 to about 100 arm and preferably 10 to 25 arm at temperatures of 175 0 C to 45O 0 C and preferably 175 0 C to 300 0 C for a time sufficient to reduce the rhenium. Then the reduced catalyst is separated from the liquid hydrocarbons for treatment according to the invention.
- the titania-supported catalyst comprising rhenium in the reduced state, and optionally, cobalt, also in the reduced state, is treated with sufficient acid to dissolve the rhenium, and also the cobalt if present, in the catalyst.
- the acid used will be a strong acid, such as, sulfuric acid, hydrochloric acid, aqua regia and nitric acid.
- the acid used will be nitric acid.
- the amount of acidic solution used will be sufficient to at least cover the catalyst and preferably will comprise a volume greater than the volume of the catalyst, for example, about 1 to about 100 times the volume of the catalyst being treated.
- the amount of acid present in the solution must be greater than the amount required to react and dissolve the metals present on the catalyst.
- the minimum amount of acid required may be estimated to be at least two moles of acid per mole of cobalt.
- An excess amount of acid is preferred to ensure rapid, complete dissolution of the metal(s).
- nitric acid is used, and the molarity of the nitric acid may range from about 0.1 to 15M, preferably from about 0.5 to 2M, most preferably from about 0.75 to IM.
- the catalyst may be treated successively with the acid.
- the treating of the catalyst may be performed at temperatures in the range of ambient to the boiling point of the acid solution, depending on acid concentration.
- the solution may be purged with air at any suitable flow rate, such as from about 5 to about 200 cc/min and, typically, about 100 cc/min.
- the acid solution containing rhenium and optionally cobalt is readily separated from the titania support by filtration. Thereafter, the resulting metal solution may be processed in order to make it suitable for use in catalyst preparation or to separate and recover the dissolved metals.
- the solution may be concentrated by evaporation or distillation and used directly in the preparation of titania-supported rhenium catalysts or cobalt and rhenium catalysts.
- the solution may be spray dried in order to recover the rhenium salt or a mixture of cobalt and rhenium salts when cobalt is present.
- the solution may be subjected to electrolysis to plate out rhenium, for example, thereby separating it from the cobaltous ions.
- the solution may be passed through an appropriate ion exchange resin to effect separation of the cobalt and rhenium.
- the cobaltous component may also be precipitated, with ammonium carbonate or a base like sodium hydroxide, and removed by filtration to provide a predominately rhenium-rich solution.
- Rhenium oxide may also be recovered by high temperature roasting of the cobalt-rhenium oxide mixture obtained by drying the solution.
- the spray dried support was calcined in a rotary calciner at 1010°C.
- the support was impregnated with an aqueous solution of cobalt nitrate and perrhenic acid and calcined in air at 454°C.
- a second impregnation and calcination was applied to produce a final catalyst containing 10.58 % Co and 1.20 % Re.
- a portion of this catalyst was reduced in hydrogen at 375°C, 1 atm, for 1 hour. For metals recovery tests, the reduced catalyst was transferred into the treating solution under argon.
- the catalyst was in the reduced state in accordance with the method of the invention.
- the catalyst was in the oxidized state.
- Run 5 the example of this invention , is the only treatment resulting in appreciable metal extraction.
- This treatment of the reduced form of the catalyst with acid produced a recovered solid with undetectable residual cobalt and low rhenium.
- the extracted metals were present in the diluted filtrate to a much greater extent compared to the other treatments.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20090717748 EP2265372A2 (en) | 2008-03-07 | 2009-03-06 | Recovery of rhenium from a rhenium-containing titania catalyst |
CA 2716315 CA2716315A1 (en) | 2008-03-07 | 2009-03-06 | Metal recovery |
AU2009220087A AU2009220087B2 (en) | 2008-03-07 | 2009-03-06 | Recovery of rhenium from a rhenium-containing titania catalyst |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US6854008P | 2008-03-07 | 2008-03-07 | |
US61/068,540 | 2008-03-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2009111076A2 true WO2009111076A2 (en) | 2009-09-11 |
WO2009111076A3 WO2009111076A3 (en) | 2009-10-29 |
Family
ID=40911928
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2009/001470 WO2009111076A2 (en) | 2008-03-07 | 2009-03-06 | Metal recovery |
Country Status (5)
Country | Link |
---|---|
US (1) | US8057572B2 (en) |
EP (1) | EP2265372A2 (en) |
AU (1) | AU2009220087B2 (en) |
CA (1) | CA2716315A1 (en) |
WO (1) | WO2009111076A2 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010102391A1 (en) * | 2009-03-13 | 2010-09-16 | Recapture Metals Limited | Rhenium recovery |
US8551212B1 (en) * | 2010-01-31 | 2013-10-08 | Behrouz Kawarizadeh | System and process for recovering base and precious metals |
US8383070B2 (en) * | 2010-03-16 | 2013-02-26 | World Resources Company | Method for recovering rhenium and other metals from rhenium-bearing materials |
US20120088306A1 (en) * | 2010-10-08 | 2012-04-12 | Basf Se | Method Of Assaying Noble Metals |
FR3013610B1 (en) * | 2013-11-27 | 2017-07-28 | Ifp Energies Now | PROCESS FOR POST-PROCESSING A CATALYST COMPRISING COBALT |
US10822674B1 (en) | 2015-01-27 | 2020-11-03 | Behrouz Kawarizadeh | System and method for recovering base and precious metals |
US9708690B2 (en) * | 2015-10-26 | 2017-07-18 | Techemet, Llc | Method for platinum recovery from materials containing rhenium and platinum metals |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2227833A (en) * | 1937-12-24 | 1941-01-07 | Chemical Foundation Inc | Method of selective extraction of metal values |
FR2671104A1 (en) * | 1990-12-28 | 1992-07-03 | Inst Francais Du Petrole | Process for antipollution treatment of a deactivated catalyst containing at least one noble metal and total recovery of the said metal and of the support alumina |
EP0568407A1 (en) * | 1992-04-21 | 1993-11-03 | Institut Francais Du Petrole | Process for reclaiming used Rhenium |
US20030119658A1 (en) * | 2001-12-21 | 2003-06-26 | Conocophillips Company | Recovery of rhenium from a spent catalyst via sublimation |
DE102005061954A1 (en) * | 2005-12-23 | 2007-07-05 | Basf Ag | Recycling of ruthenium from an used ruthenium catalyst comprises treating the catalyst containing ruthenium oxide in a hydrogen stream and treating the carrier material containing ruthenium metal with hydrochloric acid |
WO2007099365A1 (en) * | 2006-03-03 | 2007-09-07 | Johnson Matthey Plc | Catalyst reprocessing |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3578395A (en) | 1967-12-26 | 1971-05-11 | Chevron Res | Recovery of metals |
US3855385A (en) * | 1973-11-12 | 1974-12-17 | Universal Oil Prod Co | Recovery of rhenium from a spent catalyst |
DE10155237A1 (en) * | 2001-11-09 | 2003-05-22 | Starck H C Gmbh | Process for the production of rhenium |
-
2009
- 2009-02-06 US US12/322,792 patent/US8057572B2/en active Active
- 2009-03-06 AU AU2009220087A patent/AU2009220087B2/en not_active Ceased
- 2009-03-06 WO PCT/US2009/001470 patent/WO2009111076A2/en active Application Filing
- 2009-03-06 CA CA 2716315 patent/CA2716315A1/en not_active Abandoned
- 2009-03-06 EP EP20090717748 patent/EP2265372A2/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2227833A (en) * | 1937-12-24 | 1941-01-07 | Chemical Foundation Inc | Method of selective extraction of metal values |
FR2671104A1 (en) * | 1990-12-28 | 1992-07-03 | Inst Francais Du Petrole | Process for antipollution treatment of a deactivated catalyst containing at least one noble metal and total recovery of the said metal and of the support alumina |
EP0568407A1 (en) * | 1992-04-21 | 1993-11-03 | Institut Francais Du Petrole | Process for reclaiming used Rhenium |
US20030119658A1 (en) * | 2001-12-21 | 2003-06-26 | Conocophillips Company | Recovery of rhenium from a spent catalyst via sublimation |
DE102005061954A1 (en) * | 2005-12-23 | 2007-07-05 | Basf Ag | Recycling of ruthenium from an used ruthenium catalyst comprises treating the catalyst containing ruthenium oxide in a hydrogen stream and treating the carrier material containing ruthenium metal with hydrochloric acid |
WO2007099365A1 (en) * | 2006-03-03 | 2007-09-07 | Johnson Matthey Plc | Catalyst reprocessing |
Non-Patent Citations (1)
Title |
---|
RHOADS K R ET AL: "Metal recovery and catalyst reuse from the photocatalytic oxidation of copper ethylenediaminetetraacetic acid" JOURNAL OF ENVIRONMENTAL ENGINEERING, AMERICAN SOCIETY OF CIVIL ENGINEERS, US, vol. 130, no. 4, 1 April 2004 (2004-04-01), pages 425-431, XP009121368 ISSN: 0733-9372 * |
Also Published As
Publication number | Publication date |
---|---|
CA2716315A1 (en) | 2009-09-11 |
AU2009220087B2 (en) | 2013-07-11 |
US20090223325A1 (en) | 2009-09-10 |
US8057572B2 (en) | 2011-11-15 |
WO2009111076A3 (en) | 2009-10-29 |
AU2009220087A1 (en) | 2009-09-11 |
EP2265372A2 (en) | 2010-12-29 |
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